For what reason would you want to do that? If you want to store a relationship between a user and a friend (or a list of friends) you'd be better off with a one-to-many relationship.
A new table "Friends" would have 3 columns: id, user_id, friend.
Then you can insert into that Friends table and not worry about commas and such. Plus you could remove from the table and not have to worry about re-parsing the data.
Otherwise you could do something like:
UPDATE `tablename`
SET `Friends` = CONCAT(`Friends`, ', {$new_friend_name}')
WHERE `something` = 'something_else';
That's assuming you're using MySQL.